WO2016024156A1 - Procédé de régénération d'un adsorbant consommé - Google Patents

Procédé de régénération d'un adsorbant consommé Download PDF

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Publication number
WO2016024156A1
WO2016024156A1 PCT/IB2015/001355 IB2015001355W WO2016024156A1 WO 2016024156 A1 WO2016024156 A1 WO 2016024156A1 IB 2015001355 W IB2015001355 W IB 2015001355W WO 2016024156 A1 WO2016024156 A1 WO 2016024156A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
solvent
solvents
mixture
spent
Prior art date
Application number
PCT/IB2015/001355
Other languages
German (de)
English (en)
Inventor
Sergey A. ZINENKO
Elena V. ESIPOVA
Sergey I. ELKIN
Original Assignee
Ooo "Altayskiy Tzentr Prikladnoy Khimii"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ooo "Altayskiy Tzentr Prikladnoy Khimii" filed Critical Ooo "Altayskiy Tzentr Prikladnoy Khimii"
Publication of WO2016024156A1 publication Critical patent/WO2016024156A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/12—Recovery of used adsorbent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • the invention relates to a process for the rejuvenation of a spent adsorbent according to the preamble of the claim.
  • the invention is applicable to petroleum processing, and more particularly to the recovery of the spent desulfurization adsorbent used in removing heterocyclic and polyaromatic compounds from hydrocarbon fuels.
  • adsorbents used to remove heterocyclic and polyaromatic compounds from liquid hydrocarbon feedstock a heat recovery process or a solvent recovery process (extractive recovery) is used.
  • Patent RU 2448771 describes a process for the adsorption purification of hydrocarbon raw material, for the removal of thiophene and its derivatives, wherein a carrier material with gold nanoparticles applied thereon is used as the adsorbent and subsequently a refreshing of the used adsorbent is carried out by a heat-regenerating process , Refreshment is in a gas environment in a temperature range between 50 and 500 ° C, preferably between 150 and 400 ° C.
  • the gas environment may be an oxygen and helium air mixture, as well as other mixtures.
  • the deficiencies of the said regeneration process are presupposed high temperatures, the probability of detonation and burning of the adsorptive, releasing toxic gases.
  • the prior art discloses a rejuvenation of an adsorbent, namely an activated carbon fiber material having a cobalt phthalocyanine saturated thereon, saturated with mercaptans (RU 2163250).
  • the replenishment process is carried out by oxidizing mercaptans with an oxygen-containing gas at 50-80 ° C with caustic.
  • disulfides are washed out of the adsorbent by means of a hydrocarbon (n-pentane).
  • n-pentane hydrocarbon
  • the absorbed oxygen is removed from the adsorbent by treating the adsorbent with a sodium sulfide solution.
  • the disclosed heat recovery process is criticized for being very discipline-specific and aimed at the removal of only the lightest boiling mercaptans. It is finally suitable for use for gasoline.
  • Other shortcomings include the need for different reagents as well as multi-stepping of the process.
  • alkanes F. Mustafa et al. / Journal of Hazardous Materials 182 (2010) 97-107; T. Tran et al. / International Journal of Hydrogen Energy 37 (2012), 10430-10434
  • aromatic hydrocarbons toluene, xylenes, naphthalene
  • alcohols G. Blanco-Brieva et al. / Fuel 1 13 (2013), 216-220; Subhan et al.
  • the patent US 5454933 A discloses a process for the rejuvenation of the spent activated carbon adsorbent after a deep desulfurization of a distillate flow with the aid of toluene, xylene or their mixture and a recovery of Dibenzothiophen derivatives as part of the distillation of the regenerating solvent.
  • the shortcomings of the said process are a low recovery of toluene and xylenes and consequently a very high solvent consumption.
  • the same defects are also typical of an adsorption desulfurization process, in which the adsorbent used is Y-type zeolite or activated carbon or their mixture. Subsequently, the replenishment of the spent adsorbent is carried out by washing it with a solvent. Toluene, hexane, pentane, butane or their mixture can be used as solvent (WO 201 1 133631 A2).
  • the closest prior art to the invention is a process for the rejuvenation of a spent adsorbent material.
  • This method provides that the spent adsorbent is contacted with a solvent.
  • the solvent consists of at least one polar and one nonpolar solvent.
  • the polar solvent may be acetone, alcohol (isopropanol (2-propanol), ethanol, methanol), dichloromethane, ethyl acetate or their mixture.
  • the nonpolar solvent can be hexane, heptane, methylcyclopene tane, pentane, benzene, toluene, cyclohexane or their combination.
  • the regenerating solvent must have a boiling point below 80 ° C (US 2009312176 A1).
  • the known process is criticized by the fact that there is a secondary dehydration reaction on adsorbents involving the proposed solvents (alcohols, acetone).
  • the adsorbents contain silica and alumina.
  • larger unsaturated products of dehydropolycondensation are formed. This complicates the liberating process of the effective surface and requires thermal burnup of the polycondensation products.
  • the use of methanol is undesirable because of its high toxicity.
  • This object is achieved by the development of a process for the rejuvenation of a spent adsorbent which is used for desulfurization of the liquid hydrocarbon raw material by means of washing with an organic solvent.
  • the solvent is chosen from the following group: dimethylformamide, acetonitrile or their mixture or a mixture of one or two solvents selected from the group of aromatic solvents: benzene, toluene, xylene or their mixture, or it becomes any the said solvent or solvent mixtures used in combination with water.
  • the inventive method is characterized by a high efficiency of the rejuvenation of the spent adsorbent.
  • spent adsorbent active alumina was used as spent adsorbent.
  • the spent adsorbent was prepared as part of a dynamic adsorption of organic sulfur compounds from diesel oil.
  • said fuel ran at a space velocity of 2 hours -1 of the delivered fuel through a stationary adsorbent layer at 20 ° C for 5 hours.
  • the initial total sulfur in the fuel was 67 mg / kg.
  • the adsorbent utilization after the sulfur adsorption was 0.83 mg / g converted to the total sulfur.
  • a spent adsorbent was produced according to Example 1.
  • the spent adsorbent samples were used to experimentally explore a replenishment using individual solvents.
  • the solvents used were the following: dimethylformamide, acetonitrile, isopropanol (2-propanol), benzene, toluene, o-xylene, acetone.
  • Each experiment was carried out as follows: Each sample ä 10 ⁇ 0.5 g of the spent adsorbent was put a container with 50 cm 3 of solvent in each. The experiments were carried out at 20 ° C. At the end of a 1 hour interaction period, the solvent was drained and analyzed for total sulfur. The effectiveness of adsorbent rejuvenation, ie desulphurisation efficiency, was dependent on the ratio of the scrubbed sulfur to the initial total sulfur calculated on the adsorbent. The results of the experimental research are shown in Table 1.
  • the experimental research of the replenishment of a spent adsorbent was carried out similarly to Example 2, except that as a regenerating solvent, binary mixtures having a component ratio of 1: 1 (vol.) were used.
  • the binary mixtures were dimethylformamide-acetonitrile, dimethylformamide-benzene, dimethylformamide-toluene, dimethylformamide-o-xylene, acetonitrile-benzene, acetonitrile-toluene and acetonitrile-o-xylene.
  • the evaluation of the adsorbing ability of a regenerated adsorbent was carried out as follows.
  • the spent adsorbent was prepared according to Example 1.
  • a sample of 10 ⁇ 0.5 g of the spent adsorbent (this corresponds to 5 ⁇ 0.25 g of fresh adsorbent, taking into account the fact that the mass fraction of the dry adsorbent in the spent adsorbent is 50%) was placed in a container with 50 cm 3 of solvent set.
  • the solvent used was a mixture of acetonitrile and benzene with equal parts by volume of the ingredients.
  • the research was conducted at 20 ° C. After the interaction time of 1 hour, the solvent was decanted.
  • the recovered adsorbent was washed with a fresh amount of the solvent mixture to remove the residues of the contaminated regenerating solvent and the residues of the adsorbed sulfur compounds. Thereafter, the adsorbent was dried by aeration with dry hot air (90 ° C) to remove the solvent residues.
  • the Adsorbtions were carried out as follows.
  • the dried adsorbent was placed 3 of diesel oil in a container of 15 cm.
  • the total sulfur was 67 mg / kg in the fuel.
  • the diesel oil was decanted and analyzed for total sulfur.
  • the adsorption efficiency was evaluated depending on the desulfurization level, ie depending on the total sulfur content in the diesel fuel, after the adsorption has taken place. For comparison purposes, 5 ⁇ 0.25 g of fresh adsorbent set 3 of diesel oil in a container of 15 cm.
  • the total sulfur was 67 mg / kg in diesel fuel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention porte sur le traitement de pétrole brut et en particulier sur la régénération de l'adsorbant consommé. Elle concerne un procédé de régénération d'un adsorbant consommé pour la désulfuration d'hydrocarbures bruts liquides, selon lequel ledit adsorbant est lavé avec un solvant organique. On utilise comme solvant un solvant choisi dans le groupe suivant : diméthylformamide, acétonitrile ou leur mélange ou un mélange d'un ou de deux solvants, qui sont choisis dans un groupe de solvants aromatiques : benzène, toluène, xylène ou leur mélange, ou un quelconque des solvants mentionnés ou des mélanges de solvants en combinaison avec de l'eau. L'effet technique est une haute efficacité de régénération de l'adsorbant consommé.
PCT/IB2015/001355 2014-08-12 2015-08-11 Procédé de régénération d'un adsorbant consommé WO2016024156A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2014133055/04A RU2551361C1 (ru) 2014-08-12 2014-08-12 Способ регенерации отработанного адсорбента
RU2014133055 2014-08-12

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WO2016024156A1 true WO2016024156A1 (fr) 2016-02-18

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WO (1) WO2016024156A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2657342C1 (ru) * 2017-04-19 2018-06-19 Александр Юрьевич Селезнев Способ регенерации адсорбента

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5454933A (en) 1991-12-16 1995-10-03 Exxon Research And Engineering Company Deep desulfurization of distillate fuels
RU2163250C2 (ru) 1999-04-12 2001-02-20 Всероссийский научно-исследовательский институт углеводородного сырья Способ адсорбционной очистки бензинов от меркаптанов
US20050075528A1 (en) 2003-03-07 2005-04-07 Thorsten Burkhardt Proess for desulfurization, denitrating and/or dearomatization of a hydrocarbon feedstock by adsorption on a spent solid adsorbent
US20090120842A1 (en) * 2006-10-20 2009-05-14 Saudi Arabian Oil Company Process for upgrading whole crude oil to remove nitrogen and sulfur compounds
EP2133142A1 (fr) * 2008-06-11 2009-12-16 General Electric Company Système de régénération de matériau absorbant
US20110253595A1 (en) * 2010-04-20 2011-10-20 Esam Zaki Hamad Combined solid adsorption-hydrotreating process for whole crude oil desulfurization
RU2448771C1 (ru) 2008-03-10 2012-04-27 Нэшнл Инститьют Оф Эдванст Индастриал Сайенс Энд Текнолоджи Адсорбент десульфуризатор для жидких фаз

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7763163B2 (en) * 2006-10-20 2010-07-27 Saudi Arabian Oil Company Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker feedstocks

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5454933A (en) 1991-12-16 1995-10-03 Exxon Research And Engineering Company Deep desulfurization of distillate fuels
RU2163250C2 (ru) 1999-04-12 2001-02-20 Всероссийский научно-исследовательский институт углеводородного сырья Способ адсорбционной очистки бензинов от меркаптанов
US20050075528A1 (en) 2003-03-07 2005-04-07 Thorsten Burkhardt Proess for desulfurization, denitrating and/or dearomatization of a hydrocarbon feedstock by adsorption on a spent solid adsorbent
US20090120842A1 (en) * 2006-10-20 2009-05-14 Saudi Arabian Oil Company Process for upgrading whole crude oil to remove nitrogen and sulfur compounds
RU2448771C1 (ru) 2008-03-10 2012-04-27 Нэшнл Инститьют Оф Эдванст Индастриал Сайенс Энд Текнолоджи Адсорбент десульфуризатор для жидких фаз
EP2133142A1 (fr) * 2008-06-11 2009-12-16 General Electric Company Système de régénération de matériau absorbant
US20090312176A1 (en) 2008-06-11 2009-12-17 John Aibangbee Osaheni Methods and system for regeneration of adsorbent material
US20110253595A1 (en) * 2010-04-20 2011-10-20 Esam Zaki Hamad Combined solid adsorption-hydrotreating process for whole crude oil desulfurization
WO2011133631A2 (fr) 2010-04-20 2011-10-27 Saudi Arabian Oil Company Procédé combiné d'adsorption solide-hydrotraitement pour désulfuration du pétrole brut entier

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DAT T. TRAN ET AL., INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 37, 2012, pages 10430 - 10434
F. MUSTAFA ET AL., JOURNAL OF HAZARDOUS MATERIALS, vol. 182, 2010, pages 97 - 107
F. SUBHAN ET AL., FUEL PROCESSING TECHNOLOGY, vol. 97, 2012, pages 71 - 78
G. BLANCO-BRIEVA ET AL., FUEL, vol. 113, 2013, pages 216 - 220
Y. SANO ET AL., FUEL, vol. 84, 2005, pages 903 - 910

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